Basic dyeable polymer of polyethylene terephthalate shaped article containing 0.5 percent of a sulfonated pyrrole

ABSTRACT

A polyethylene terephthalate shaped article containing a sulfonated pyrrole and permeated uniformly throughout by a cationic dye.

United States Patent Stackman et al.

[ 51 May 9,1972

[54] BASIC DYEABLE POLYMER OF POLYETHYLENE TEREPHTHALATE SHAPED ARTICLECONTAINING 0.5 PERCENT OF A SULFONATED PYRROLE [72] Inventors: Robert W.Stackman, Morristown, N.J.;

Donald E. Sargent, Schenectady, NY.

[52] U.S. C1 ..8/168, 8/178, 8/180, 8/179, 260/75, 260/78, 260/93.7

[51] Int. Cl. ..D06p 5/06 [58] Field of Search ..8/168, 179; 260/75,78.5, 78

[56] References Cited UNITED STATES PATENTS 3,018,272 1/1962 Griffing2,952,506 9/1960 Dellis ..8/168 Primary Examiner-George F. LesmesAssistant Examiner-B. Bettis Attorney-Thomas J. Morgan, Stephen D.Murphy and Robert J. Blanke [5 7] ABSTRACT A polyethylene terephthalateshaped article containing a suifonated pyrrole and permeated uniformlythroughout by a cationic dye.

5 Claims, No Drawings BASIC DYEABLE POLYMER OF POLYETHYLENETEREPI'ITHALATE SHAPED ARTICLE CONTAINING 0.5 PERCENT OF A SULFONATEDPYRROLE This invention, which is a divisional application of copendingapplication Ser. No. 605,570 filed December 29, 1966, now US. Pat.3,507,835.

The invention relates to compositions and shaped articles madetherefromhaving improved dyeability properties and methods of producingthese products. More particularly, the invention is directed tocompositions of synthetic polymers, preferably synthetic linearthermoplastic polymers containing a specific type of sulfonated pyrrolewhich in turn can provide articles such as films, fibers and the like,having an affinity for basic dyes.

Successful methods have been suggested in the past to improve thedyeability of shaped articles made from synthetic polymers such asfibers, fabrics or films especially utilizing basic dyes to providebrighter colors and also to permit cross dyeing of the articles. Thesemethods utilize the techniques of incorporating sulfonated monomers intosynthetic polymers such as acetate, triacetate, acrylic, modacrylic,polyester, nylon, polypropylene and the like to provide copolymers.Typical of this procedure is US. Pat. No. 3,018,272 which describes theprocess of producing basic dyeable polyesters having incorporatedtherein as monomers, the sulfonated monomers. Although these copolymersprovide satisfactory basic dyeable materials, other suitable materialsare being sought to provide improvements in dyeability for the syntheticlinear thermoplastic polymers.

It has now been discovered that a certain type of sulfonated pyrrole canbe incorporated, i.e., in the form of a copolymer or additive intosynthetic polymers, to improve the basic dye uptake of these polymersand end products made therefrom. The specific type of sulfonated pyrrolewhich can be utilized can be represented by the following formula:

wherein each R, individually, represents hydrogen or an alkyl groupcontaining from one to six carbon atoms; each R, individually,represents hydrogen and an alkyl group containing from one to six carbonatoms; Ar represents an arylene radical and X represents a metal tosatisfy the valence of the sulfonate group and preferably represents analkali metal. It is usually desirable to use at least about 0.5 weightpercent of the sulfonated pyrrole based on the total polymer to providebasic dye sites. Polymer compositions having a sulfonated pyrrolecontent lower than 0.5 weight percent will have only a relatively lowaffinity for basic dyes. Polymer compositions containing about 10 weightpercent of the sulfonated pyrrole compound have a very high affinity forbasic dyes. Higher concentrations will not lead to appreciable increasesin basic dyeability and in general may unduly affect tenacity in theshaped articles. The sulfonated pyrrole compound concentrations in therange from 2 to 8 weight percent of the total polymer, are preferred.The sulfonated pyrrole compound can be added to the polymerizationreaction or to the starting materials such as are used in the esterinterchange reaction if this is required. If the presence of thesesulfonated pyrrole compounds in the polymer are desired to be in theform of copolymers the addition can occur very early in thepolymerization or in the initial starting materials. If it is desired tohave the sulfonated pyrrole compounds in the polymer as merely additivesthen the materials should be added at the later stages ofpolymerization.

The sulfonated pyrrole compound can be prepared according to theprocedure described in Journal Fur Praktische Chemie 17, 213 (1962).This procedure involves the typical reaction such as equimolar amountsof the sodium salt of sulfanilic acid and diethyl diacetyl succinate inacetic acid. Under these conditions, l-(p-sodium sulfophenyl)-2,5-dimethyl-3,4-dicarbo-ethoxy pyrrole is produced.

In the preparation of the sulfonated pyrrole compounds, typical startingmaterials include, among others: diethyldiacetyl succinate; dipropyldipropionyl succinate; di)n-butyl) di(n-butyryl) succinate; di(n-pentyl)diisovaleryl succinate; di(n-hexyl) di(n-caproyl) succinate; and thelike. Typical alkali salts of sulfanilic acid include, among others:sodium 4- aminophenyl sulfonate; potassium 4-aminophenyl sulfonate;lithium 4-aminophenyl sulfonate; sodium 4-aminonaphthyl 1- sulfonate;potassium3-aminonaphthyl l-sulfonate; lithium 8- aminonaphthyll-sulfonate; alkyl substituted sulfanilic acid alkali salts; alkylsubstituted aminonaphthyl sulfonic acid alkali salts; halogensubstituted sulfanilic acid alkali salts and the like. The metals whichcan be used to satisfy the valence of the sulfonate group can includethe alkali metals such as sodium, potassium, lithium and the like,alkali earth metals such as calcium, strontium, barium and the like ormetals such as magnesium, cobalt, manganese and the like. The preferredmetals, however, include the alkali metals.

The new compositionsof the present invention, i.e., containingsulfonated pyrrole compounds and polymerized synthetic linearthermoplastic polymer, are useful in the production of shaped articlesby extrusion, molding, casting or the like. These shaped articles inturn may be formed in fibers (filaments and staple), fabrics, ornaments,films and the like.

The term linear thermoplastic polymer as used herein includes polymericpolymethylene terephthalates, especially preferred is polyethyleneterephthalate. Other polymers-which can be included herein utilizedherein are polyalkylene terephthalate containing modifiers such asdibasic acids including among others; isophthalic acid, sebacic acid,adipic acid and the like. Cyclic glycols can also be substituted for thealkylene glycols in the linear terephthalate polymers. Other polymersincluded herein are polyamides such as polyhexamethylene adipamide,polyhexamethylene sebacamide, polytetramethylene sebacamide,polytetramethylene adipamide andthe like. Other polyamides include thoseprepared from di(4-amino-cyclohexyl) ethane or1,6-(4-aminocyclohexyl)hexane as the diamine components. Additionalpolymers include polypropylene, polybutenes and the like. As is known,the intrinsic viscosities of the above-described polymers should be inexcess of 0.2, preferably in the range from 0.4 to 1.0 when used forproducing textile and industrial products. The measurement of intrinsicviscosity is conducted by utilization of a one-weight percent polymersolution in a mixture of 58.8 parts of phenol and 41.2 parts oftrichlorophenol.

Various other materials may be present in the present new compositions.For example, such ester exchange catalysts as salts of calcium,magnesium, manganese and the like and such polymerization catalysts asantimony oxide, antimonic acid or the like, may be used. In addition,pigments, delusterants, or other additives such as titanium dioxide orbarium carbonate.

The yarns or filaments produced in accordance with the present inventionare suitable for the usual textile applications. They may be employed inthe knitting or weaving of fabrics of all types as well as in theproduction of nonwoven, felt-like products produced by known methods.Their physical properties closely parallel those of their relatednon-modified polymer fibers. However, they have particular sensitivitytoward basic dyes. By a basic dye" is meant a colored cationic organicsubstance such as those containing sulfonium, oxonium or quaternaryammonium functional groups. Among the basic types which may be appliedto the filaments formed in accordance with the present invention may bementioned Victoria Green WB (0.1. 657); Thodiamine B (01. 749);Brilliant Green B (C1. 662); Victoria Pure Blue BO(Pr 198); Sevron Blue8; and the like. The dyes are preferably applied from an aqueoussolution at a temperature between and C.

EXAMPLE i,

In a reaction flask, 19.5 grams (0.] mol) of the sodium salt ofsulfanilic acid and 25.8 grams (0.1 mol) diethyl diacetyl succinate areheated in 800 milliliters of acetic acid for 2 hours at 80 C. Thereaction product (l-(p-sodiumsulfophenyl)-2,5-dimethyl-3,4-dicarboethoxy pyrrole) is cooled and etheradded thereto. The reaction product is precipitated and recovered byfiltration. The product is recrystallized in a small amount of acetoneto obtain a white salt 'having a melting point of 3 l3l 1 C. The amountof product obtained was 35 grams representing a yield of 84 percent.

EXAMPLE 2 To a 500 ml. three-necked flask equipped with stirrer,nitrogen inlet and distillation head were added 3.89 g. of l-(psodiumsulfophenyl)-2,5-dimethyl-3,4-dicarboethoxy pyrrole in 20 ml of ethyleneglycol, 0.07 g. antimonic acid and 100 g. bis(hydroxyethyl)terephthalate. The flask was flushed three times with nitrogen, thenheated to 235 C., at which temperature all the material had melted toform a clear solution. The temperature was increased over a period of 1hour to 270 C. The pressure was then slowly loweredby means of a vacuumpump to 0.25 mm Hg while the temperature was increased to 290 C. Thepolymerizing mixture was stirred at 290 C. and 0.25 mm Hg pressure for90 minutes. At the end of this period, the vacuum was released and thepolymer allowed to cool. The recovered polymer had a crystalline meltingpoint of 248-25 1 C. and had an inherent viscosity of 0.47 determined ina mixture of 58.8 parts phenol and 41.2 parts trichlorophenol. Thepolymer was spun at 285 C. from a melt index apparatus and oriented bystretching over a heated surface. A sample of the oriented fiber wasdyed in a Sevron Blue B basic dye bath for 1 hour at C.The fibers dyedto a deep shade of blue having good washfastness properties.

In a similar manner as above, polyhexamethylene adipamide can besubstituted for polyethylene terephthalate.

It is understood that the foregoing description is merely illustrativeof preferred embodiments of the invention of which many variations maybe made by those skilled in the art within the scope of the followingclaims without departing from the spirit thereof.

WHAT IS CLAIMED IS:

1. A polyethylene terephthalate shaped article containing at least 0.5weight percent of a sulfonate having the formula:

wherein R, each individually, represents hydrogen and alkyl groupcontainingfrom one to six carbon atoms, R each individually, representshydrogen and an alkyl group containing from one to six carbon atoms, Arrepresents a phenylene or a naphthalene radical and X represents a metalto satisfy the available valence selected from the group consisting ofan alkali metal, an alkali earth metal, magnesium, cobalt and manganese,said shaped article permeated uniformly throughout by a cationic dye,the said dye being bound in the shaped article b the available groups inthe sha ed article.

2. e shaped article of claim 1 w erein X represents an alkali metal.

3. The shaped article of claim 2 wherein the sulfonate is present inamounts ranging from 2 to 8 weight percent.

4. The shaped article of claim 2 wherein the sulfonate present isl-(p-sodium sulfophenyl)-2,5-dimethyl-3,4-dicarboethoxy pyrrole.

5. A polyethylene terephthalate fiber having an intrinsic viscosity ofat least 0.4 measured in a mixture of 58.8 parts of phenol and 41.2parts of trichlorophenol wherein said fiber contains l-(p-sodiumsulfophenyl)-2,5?dimethyl-3,4-dicarboethoxy pyrrole in amounts rangingfrom about 2 weight percentage to about 8 weight percentage based on thetotal fiber, said fiber permeated uniformly throughout by a cationicdye, the said dye being bound in the fiber by the available groups inthe fiber.

2. The shaped article of claim 1 wherein X represents an alkali metal.3. The shaped article of claim 2 wherein the sulfonate is present inamounts ranging from 2 to 8 weight percent.
 4. The shaped article ofclaim 2 wherein the sulfonate present is 1-(p-sodiumsulfophenyl)-2,5-dimethyl-3,4-dicarboethoxy pyrrole.
 5. A polyethyleneterephthalate fiber having an intrinsic viscosity of at least 0.4measured in a mixture of 58.8 parts of phenol and 41.2 parts oftrichlorophenol wherein said fiber contains 1-(p-sodiumsulfophenyl)-2,5-dimethyl-3,4-dicarboethoxy pyrrole in amounts rangingfrom about 2 weight percentage to about 8 weight percentage based on thetotal fiber, said fiber permeated uniformly throughout by a cationicdye, the said dye being bound in the fiber by the available groups inthe fiber.